JP6617905B2 - Polyarylene sulfide film and method for producing the same - Google Patents

Description

  The present invention relates to a polyarylene sulfide film and a method for producing the same.

  In recent years, in various fields including the electrical and electronic parts field, there has been an active movement toward low halogen as an environmental measure.

  A polyarylene sulfide resin (hereinafter sometimes abbreviated as “PAS resin”) represented by a polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”) has heat resistance, chemical resistance, electrical insulation, etc. It is attracting attention as a halogen-free material because it is excellent in that it has high flame retardancy without using a halogen-based flame retardant.

  Paying attention to the excellent characteristics of the PAS resin as described above, various application developments have been attempted.

  Conventionally, a polyphenylene sulfide resin is produced by solution polymerization in which, for example, p-dichlorobenzene and sodium sulfide, or sodium hydrosulfide and sodium hydroxide are used as raw materials in a polymerization reaction in an organic polar solvent (for example, patents). References 1 and 2). Currently commercially available polyphenylene sulfide resins are generally produced by this method.

  However, it is difficult to obtain a high molecular weight body by this method. Considering forming into a film or the like, there are cases where the amount of low molecular weight is large and the processability is not sufficient. As a method for improving this, generally, an elastomer component or the like is added or used in combination. (For example, patent document 3). In addition, since the polyphenylene sulfide resin is a polymer having a high degree of crystallinity, addition of a plasticizer or the like is required to improve processability even when the polymerization conditions are adjusted to obtain a high molecular weight product.

  Patent Document 4 discloses a method of adding a predetermined amount of cyclic polyphenylene sulfide for the purpose of improving moldability and yield. Patent Document 5 discloses a biaxially oriented polyarylene sulfide film composed only of a polyarylene sulfide resin and particles as a composite material that suppresses heat resistance, moldability, and mold contamination.

  On the other hand, in the electric and electronic parts industry, from the viewpoint of environmental protection, the movement of halogen regulation is rapidly expanding, and the regulation (900 ppm or less) is applied to the halogen in the material. As a method for improving this, as a method for obtaining a PAS with a reduced halogen content, for example, a method in which a cyclic arylene sulfide oligomer is heated and subjected to ring-opening polymerization in the presence of a ring-opening polymerization catalyst is disclosed (for example, (See Patent Documents 6 and 7.)

US Pat. No. 2,513,188 US Pat. No. 2,583,941 JP 2006-143793 A JP 2012-233302 A JP 2010-242066 A JP-A-5-163349 JP 2010-126621 A

However, in the above method, it may be difficult to produce a polyarylene sulfide film having good processability while maintaining the original characteristics of the polyarylene sulfide resin such as heat resistance.
In addition, the method described in Patent Document 6 has a problem that it is difficult to selectively synthesize cyclic arylene sulfide oligomers, and the method described in Patent Document 7 can somewhat reduce halogen. In a film mainly composed of a resin, it is difficult to satisfy the halogen content regulation value (900 ppm or less).

  Therefore, the main problem to be solved by the present invention is that the amount of halogen is small, it can be easily processed while maintaining the original characteristics of polyarylene sulfide resin, and the occurrence of film breakage during film formation is sufficiently suppressed. It is providing the polyarylene sulfide resin which consists of a polyarylene sulfide resin which can be manufactured or a composition containing this, and its manufacturing method.

  As a result of various studies, the present inventors have reacted sulfoxide with an aromatic compound to obtain poly (arylenesulfonium salt), and dealkylated or dearylated the poly (arylenesulfonium salt). A polyarylene sulfide resin comprising a step of obtaining a polyarylene sulfide resin and a polyarylene sulfide resin obtained by a method comprising the composition or a composition comprising the same, and a method for synthesizing the polyarylene sulfide resin from a different reaction route The synthesis has found that the above problems can be solved, and the present invention has been completed.

That is, the present invention is a polyarylene sulfide film comprising a polyarylene sulfide resin or a composition containing the same, wherein the polyarylene sulfide resin comprises a sulfoxide represented by the following general formula (1) and the following general formula (2 And a poly (arylenesulfonium salt) having a structural unit represented by the following general formula (10):
Dealkylating or dearylating the poly (arylenesulfonium salt) to obtain a polyarylene sulfide resin having a structural unit represented by the following general formula (20);
Are those that can be obtained by a method comprising the polyarylene sulfide resin, the infrared absorption spectrum measured by FT-IR ^{spectroscopy,} one having an absorption peak in the range of 2910cm ^-1 ~2930cm -1 A polyarylene sulfide film is provided.

(In Formula (1), (2), (10) or (20), R ¹ is an aryl optionally having an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. R ^2a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, —Ar ⁴ , —S—Ar ⁴ , —O—Ar ⁴ , —CO—Ar ⁴ , —SO ₂ —Ar ⁴ or represents ^{_{-C (CF 3) 2 -Ar 4}} , R 2b is a direct ^{bond, -Ar 6 -, - S-} Ar 6 -, - O-Ar 6 -, - CO-Ar 6 -, - SO 2 - Ar ⁶ — or —C (CF ₃ ) ₂ —Ar ⁶ — is represented, Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ each independently represent an arylene group which may have a substituent, Ar ^3a and Ar ⁴ each independently represent an aryl group which may have a substituent, Z is a direct bond, - -, - O -, - CO -, - SO 2 - or -C _{(CF 3) 2} - represents, X ^- represents an anion).

According to the present invention, from the polyarylene sulfide resin that can be easily processed while maintaining the original characteristics of the polyarylene sulfide resin and can be produced with sufficiently suppressed occurrence of film breakage during film formation, or a composition containing the same. The polyarylene sulfide film and the manufacturing method thereof can be provided.
Moreover, the amount of halogen in the resin can be remarkably suppressed, and it is possible to meet the recent demand for reducing the environmental load. Furthermore, the resin used in the present application also has good processability.
In the conventional polymerization method, the amount of gas generated by heating is relatively large. In particular, when spinning by melt spinning or the like, the problem of gas generation tends to become remarkable because heating is performed at a temperature higher than the melting point of the polyarylene sulfide resin. However, since the polyarylene sulfide resin according to the present invention suppresses the amount of gas generated during heating to a low level, it can sufficiently suppress deterioration in film quality caused by gas generation.
Furthermore, the present invention is superior not only in the amount of the generated gas but also in quality. According to the present invention, since the terminal of the main chain of polyarylene sulfide is blocked with Me, the terminal does not become SH or the like unlike the conventional polymerization method. For this reason, thiophenol, a chloro compound, etc. do not generate | occur | produce on the mechanism of superposition | polymerization, but it leads to the improvement of a working environment.
Further, since the terminal of the main chain of polyarylene sulfide is Me, the polarizability is lower than in the case of SH as in the conventional polymerization method, so that components that cause gas generation are removed during the washing process. Cheap. For this reason, it contributes to cost reduction, such as introduction of new facilities.

It is a figure showing the infrared absorption spectrum which measured the PPS resin of the synthesis example 1 by FT-IR spectroscopy. It is a figure showing the infrared absorption spectrum which measured the PPS resin of the synthesis example 2 by FT-IR spectroscopy. It is a figure showing the infrared absorption spectrum which measured the PPS resin of the synthesis example 3 by FT-IR spectroscopy. It is a figure showing the infrared absorption spectrum which measured the PPS resin of the comparative synthesis example by FT-IR spectroscopy.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The polyarylene sulfide film according to this embodiment is a film made of a polyarylene sulfide resin or a composition containing the same.

The polyarylene sulfide resin used in the present embodiment comprises a step of reacting a sulfoxide and an aromatic compound to obtain a poly (arylenesulfonium salt), a dealkylation or dearylation of the poly (arylenesulfonium salt), And obtaining a polyarylene sulfide resin. According to such a method, a polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with conventional methods such as the Philips method.
The sulfoxide used in the present embodiment is a compound represented by the following general formula (1), and has two sulfinyl groups.

In General Formula (1), R ¹ represents an aryl group which may have an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and Ar ¹ and Ar ² are each represented by Independently, it represents an arylene group which may have a substituent, and Z represents a direct bond, —S—, —O—, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —. In the general formula (1), when Z is —S—, R ¹ is an alkyl group having 2 to 10 carbon atoms or an aryl group optionally having an alkyl group having 2 to 10 carbon atoms. There may be.

  The sulfoxide represented by the general formula (1) can be obtained, for example, by oxidizing the compound represented by the following general formula (3) by reacting with an oxidizing agent or the like.

In the general formula ^(3), R ^1, Ar 1, Ar ² and Z are defined above for the ^{R 1,} Ar 1, Ar ² and Z in the general formula (1).

  The oxidizing agent is not particularly limited, and various oxidizing agents can be used. As the oxidizing agent, for example, potassium permanganate, oxygen, ozone, organic peroxide, hydrogen peroxide, nitric acid, meta-chloroperoxybenzoic acid, oxone (registered trademark), osmium tetroxide and the like can be used.

  If necessary, the compound represented by the general formula (3) may be substituted with a halogen atom represented by Y and a sulfide group using a compound represented by the following general formula (4) and dimethyl disulfide. By doing so, a sulfide compound can be synthesized.

In the general formula (4), Y represents a halogen ^atom, Ar 1, Ar ² and Z are defined above for the ^Ar 1, Ar ² and Z in the general formula (1). Y is, for example, a chlorine atom, a bromine atom, an iodine atom or the like, and is preferably a chlorine atom.

In the compound represented by the general formula (1), (3) or (4), Ar ¹ and Ar ² may be an arylene group such as phenylene, naphthylene, biphenylene and the like. Ar ¹ and Ar ² may be the same or different, but are preferably the same.

Aspects of binding of Ar ¹ and Ar ² is not particularly limited, in the arylene group is preferably one that binds at positions remote. For example, when Ar ¹ and Ar ² are phenylene groups, they are preferably a unit bonded at the para position (1,4-phenylene group) and a unit bonded at the meta position (1,3-phenylene group). More preferred are units bonded at the position. It is preferable in terms of heat resistance and crystallinity of the resulting resin to be composed of units bonded at the para position.

When the arylene group represented by Ar ¹ or Ar ² has a substituent, the substituent is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. It is preferably an alkyl group having 1 to 10 carbon atoms such as a group, a hydroxy group, an amino group, a mercapto group, a carboxyl group or a sulfo group.

  Examples of the compound represented by the general formula (1) include 4,4′-bis (methylsulfinyl) biphenyl, bis [4- (methylsulfinyl) phenyl] ether, and bis [4- (methylsulfinyl) phenyl] sulfide. Bis [4- (methylsulfinyl) phenyl] sulfone, bis [4- (methylsulfinyl) phenyl] ketone, 2,2-bis [4- (methylsulfinyl) phenyl] -1,1,1,3,3, Examples include 3-hexafluoropropane. These compounds can be used alone or in combination.

Examples of R ¹ include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Aryl groups having a structure such as naphthyl, biphenyl and the like, and the aryl group includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group It may have an alkyl group having 1 to 10 carbon atoms such as 1 to 4 on the aromatic ring as a substituent.

  The aromatic compound used in this embodiment is represented by the following general formula (2), for example.

In General Formula (2), R ^2a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, —Ar ⁴ , —S—Ar ⁴ , —O—Ar ⁴ , —CO—Ar ⁴ , —SO ₂ —. Ar ⁴ or —C (CF ₃ ) ₂ —Ar ⁴ is represented, and Ar ^3a and Ar ⁴ each independently represent an aryl group which may have a substituent. When R ^2a is an alkyl group having 1 to 10 carbon atoms, examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. It is done. When the aryl group represented by Ar ^3a or Ar ⁴ has a substituent, the substituent is preferably an alkyl group (such as a methyl group), a hydroxy group, an amino group, a mercapto group, a carboxyl group, or a sulfo group. . Ar ^3a and Ar ⁴ include, for example, an aryl group having a structure such as phenyl, naphthyl, or biphenyl, and the aryl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. , An octyl group, a nonyl group, a decyl group or the like, and an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an amino group, a mercapto group, a carboxy group, and a sulfo group. Good. Ar ^3a and Ar ⁴ may be the same or different, but are preferably the same.

  Examples of the compound represented by the general formula (2) include benzene, toluene, biphenyl, diphenyl sulfide, diphenyl ether, benzophenone, diphenyl sulfone, hexafluoro-2,2-diphenylpropane, and the like. Of these compounds, biphenyl, diphenyl sulfide or diphenyl ether is preferred from the viewpoint of crystallinity. From the viewpoint of obtaining a polyarylene sulfide resin as a higher molecular weight, diphenyl sulfide is preferable. Diphenyl sulfide also has a low melting point and can itself function as a solvent, and is preferable from the viewpoint of controlling the reaction temperature. From the viewpoint of reducing the melting point of the polyarylene sulfide resin, diphenyl ether is preferred. From the viewpoint of improving the heat resistance of the polyarylene sulfide resin, benzophenone is preferable. From the viewpoint of obtaining an amorphous polyarylene sulfide resin, diphenyl sulfone or hexafluoro-2,2-diphenylpropane is preferable. By making it amorphous, it is possible to improve the molding processability and transparency of the polyarylene sulfide resin.

  The reaction between the sulfoxide and the aromatic compound is preferably performed in the presence of an acid. As the acid, either an organic acid or an inorganic acid can be used. Examples of the acid include non-oxygen acids such as hydrochloric acid, hydrobromic acid, hydrocyanic acid, and tetrafluoroboric acid; sulfuric acid, phosphoric acid, perchloric acid, bromine forged, nitric acid, carbonic acid, boric acid, molybdic acid, isopolyacid, and heteropolyacid. Inorganic oxo acids such as acids; sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropolyacid salts, partial salts or esters of sulfuric acid such as monomethyl sulfuric acid, trifluoromethane sulfuric acid; formic acid, acetic acid, propionic acid, butanoic acid, succinic acid Monovalent or polyvalent carboxylic acids such as acid, benzoic acid and phthalic acid; halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid and trifluoroacetic acid; methanesulfonic acid and ethanesulfone Acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethyl Monovalent or polyvalent sulfonic acids such as sulfonic acid and benzenedisulfonic acid; partial metal salts of polyvalent sulfonic acid such as sodium benzenedisulfonate; antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tetrachloride Examples include Lewis acids such as tin, zinc chloride, copper chloride, and iron chloride. Of these acids, trifluoromethanesulfonic acid and methanesulfonic acid are preferably used from the viewpoint of reactivity. These acids may be used alone or in combination of two or more.

  Since this reaction is a dehydration reaction, a dehydrating agent may be used in combination. Examples of the dehydrating agent include phosphoric anhydrides such as phosphorus oxide and diphosphorus pentoxide; sulfonic acids such as benzenesulfonic anhydride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, and paratoluenesulfonic anhydride. Anhydrides; carboxylic acid anhydrides such as acetic anhydride, fluoroacetic anhydride, and trifluoroacetic anhydride; anhydrous magnesium sulfate, zeolite, silica gel, calcium chloride, and the like. These dehydrating agents may be used alone or in combination of two or more.

  A solvent can be appropriately used for the reaction between the sulfoxide and the aromatic compound. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol and isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitrile solvents such as acetonitrile, and halogen-containing solvents such as methylene chloride and chloroform. Solvents, saturated hydrocarbon solvents such as normal hexane, cyclohexane, normal heptane, cycloheptane, amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, sulfur-containing solvents such as sulfolane and DMSO, tetrahydrofuran, dioxane, etc. And ether-based solvents. These solvents may be used alone or in combination of two or more.

  In the step of obtaining a poly (arylenesulfonium salt) by reacting a mixture containing a sulfoxide and an aromatic compound, the conditions can be appropriately adjusted so that the reaction proceeds appropriately. The reaction temperature is preferably in the range of −30 to 150 ° C., more preferably in the range of 0 to 100 ° C.

  The poly (arylenesulfonium salt) obtained by the above process has a structural unit represented by the following general formula (10).

In the general formula ^{(10), R 2b} represents a direct ^{bond, -Ar 6 -, - S-} Ar 6 -, - O-Ar 6 -, - CO-Ar 6 -, - SO 2 -Ar 6 - or -C (CF ₃ ) ₂ —Ar ⁶ —, Ar ^3b and Ar ⁶ each independently represent an arylene group which may have a substituent, X ⁻ represents an anion, Ar ¹ , Ar ² , R ¹ and Z are defined above for the ^{Ar 1,} Ar 2, ^{R 1} and Z in the general formula (1). Ar ^3b and Ar ⁶ may be, for example, an arylene group such as phenylene, naphthylene, and biphenylene. Ar ^3b and Ar ⁶ may be the same or different, but are preferably the same. Examples of X ⁻ representing an anion include anions such as sulfonate, carboxylate, and halogen ion. In the general formula (10), when Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups and R ^2b is a direct bond, Z is a direct bond, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —, Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups, R ^2b is —Ar ⁶ —, and Ar ⁶ is 1,4-phenylene group. Sometimes Z may be —S—, —O—, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —.

In the structural unit represented by the general formula (10), the bonding mode of Ar ^3b and Ar ⁶ is not particularly limited, and Ar ¹ and Ar ^{2 in the} general formulas (1), (3), and (4) Similar considerations can be applied to the combination aspect of.

When the arylene group represented by Ar ^3b or Ar ⁶ has a substituent, the substituent is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl It is preferably an alkyl group having 1 to 10 carbon atoms such as a group, a hydroxy group, an amino group, a mercapto group, a carboxyl group or a sulfo group. However, the proportion of the structural unit of the general formula (10) in which Ar ¹ , Ar ² , Ar ^3b, and Ar ⁶ are arylene groups having a substituent suppresses a decrease in crystallinity and heat resistance of the polyarylene sulfide resin. From the viewpoint, it is preferably in the range of 10% by mass or less, more preferably 5% by mass or less, based on the whole poly (arylenesulfonium salt).

  The structural unit possessed by the poly (arylenesulfonium salt) includes, for example, a sulfoxide represented by the general formula (1) and an aromatic represented by the general formula (2) in accordance with the purpose of using the polyarylene sulfide resin. It can select suitably by changing the combination with a compound.

  The method for producing a polyarylene sulfide resin according to this embodiment includes a step of dealkylating or dearylating poly (arylenesulfonium salt). The dealkylation or dearylation of poly (arylenesulfonium salt) is considered to proceed, for example, as represented by the following reaction formula.

  In this step, a dealkylating agent or a dearylating agent can be used. The dealkylating agent or dearylating agent includes a nucleophile or a reducing agent. As the nucleophilic agent, a nitrogen-containing aromatic compound, an amine compound, an amide compound, or the like can be used. As the reducing agent, metallic potassium, metallic sodium, potassium chloride, sodium chloride, hydrazine and the like can be used. These compounds may be used alone or in combination of two or more.

  Examples of the aromatic compound include pyridine, quinoline, aniline and the like. Of these compounds, pyridine which is a general-purpose compound is preferable.

  Examples of the amine compound include trialkylamine and ammonia.

  As the amide compound, an aromatic amide compound or an aliphatic amide compound can be used. The aliphatic amide compound is represented, for example, by a compound represented by the following general formula (30).

In General Formula (30), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹¹ and R ¹³ are bonded to form a cyclic structure. It may be. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

  The compound represented by the general formula (30) is, for example, dealkylated by dealkylating or dearylating an alkyl group or aryl group bonded to a sulfur atom of a sulfonium salt as represented by the following reaction formula: It is thought to function as a de- or dearylating agent.

  Furthermore, the aliphatic amide compound is more miscible with water than the aromatic amide compound, and can be easily removed by washing the reaction mixture with water. For this reason, compared with the case where an aromatic amide compound is used, the residual amount of the aliphatic amide compound in polyarylene sulfide resin can be reduced.

  As described above, when the aliphatic amide compound is used as a dealkylating agent or a dearylating agent, it suppresses gas generation during resin processing, improves the quality of the polyarylene sulfide resin molded product, improves the working environment, and It is preferable because the maintainability of the mold can be improved. In addition, since the aliphatic amide compound is also excellent in the solubility of the organic compound, the use of the aliphatic amide compound makes it possible to easily remove the oligomer component of polyarylene sulfide from the reaction mixture. As a result, it is possible to synergistically improve the quality of the polyarylene sulfide resin obtained by removing the oligomer component, which may contribute to gas generation, with the aliphatic amide compound.

Examples of such aliphatic amide compounds include primary amide compounds such as formamide, secondary amide compounds such as β-lactam, N-methyl-2-pyrrolidone, dimethylformamide, diethylformamide, dimethylacetamide, and tetramethylurea. A tertiary amide compound such as can be used. The aliphatic amide compound preferably includes an aliphatic tertiary amide compound in which R ¹² and R ¹³ are aliphatic groups from the viewpoint of solubility of poly (arylenesulfonium salt) and solubility in water. Among the amide compounds, N-methyl-2-pyrrolidone is preferable.

  In addition to functioning as a dealkylating agent or dearylating agent, the aliphatic amide compound can also be used as a reaction solvent because of its excellent solubility. Therefore, the amount of the aliphatic amide compound used is not particularly limited, but the lower limit is preferably in the range of 1.00 equivalents or more with respect to the total amount of poly (arylenesulfonium salt), and 1.02 equivalents. The above range is more preferable, and the range of 1.05 equivalents or more is more preferable. If the amount of the aliphatic amide compound used is 1.00 equivalent or more, the poly (arylenesulfonium salt) can be sufficiently dealkylated or dearylated. On the other hand, the upper limit is preferably 100 equivalents or less, and more preferably 10 equivalents or less. Only an aliphatic amide compound may be used as the reaction solvent, or another solvent such as toluene may be used in combination.

  The conditions for reacting the poly (arylenesulfonium salt) and the aliphatic amide compound according to this embodiment can be appropriately adjusted so that dealkylation or dearylation proceeds appropriately. The reaction temperature is preferably in the range of 50 to 250 ° C, more preferably in the range of 80 to 220 ° C.

  The method for producing a polyarylene sulfide resin according to this embodiment may further include a step of washing the polyarylene sulfide resin with water, a water-soluble solvent, or a mixed solvent thereof. By including such a washing step, the remaining amount of the dealkylating agent or dearylating agent contained in the obtained polyarylene sulfide resin can be more reliably reduced. This tendency becomes remarkable when an aliphatic amide compound is used as a dealkylating agent or a dearylating agent.

  By passing through the washing step, it is possible to more reliably reduce the remaining amount of the dealkylating agent or dearylating agent in the polyarylene sulfide resin obtained. The residual amount of the dealkylating agent or dearylating agent in the resin is in the range of 1000 ppm or less based on the mass of the resin containing the polyarylene sulfide resin and other components such as the dealkylating agent or the dearylating agent. Preferably, the range is 700 ppm or less, and more preferably 100 ppm or less. By setting it as 1000 ppm or less, the substantial influence with respect to the quality of the polyarylene sulfide resin obtained can be reduced.

  The solvent used in the washing step is not particularly limited, but is preferably a solvent that dissolves unreacted substances. Examples of the solvent include acidic aqueous solutions such as water, aqueous hydrochloric acid, aqueous acetic acid, aqueous oxalic acid, and aqueous nitric acid, aromatic hydrocarbon solvents such as toluene and xylene, and alcohols such as methanol, ethanol, propanol, and isopropyl alcohol. Solvents, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitrile solvents such as acetonitrile, ether solvents such as tetrahydrofuran and dioxane, amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, dichloromethane And halogen-containing solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, water and N-methylpyrrolidone are preferred from the viewpoint of removal of the reaction reagent and removal of the oligomer component of the resin.

  The polyarylene sulfide resin obtained by the production method according to this embodiment has a structural unit represented by the following general formula (20).

In the general formula ^{(20), R 2b, Ar} 1, Ar 2, Ar 3b and Z, ^R 2b in the formula ^(10), is similarly defined as ^{Ar 1,} Ar 2, Ar ^3b and Z. In the general formula (20), when Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups and R ^2b is a direct bond, Z is a direct bond, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —, Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups, R ^2b is —Ar ⁶ —, and Ar ⁶ is 1,4-phenylene group. Sometimes Z may be —S—, —O—, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —.

In the structural unit represented by the general formula (20), the bonding mode of Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ is not particularly limited, and the general formulas (1), (3) and (4) The same idea as that of the bonding mode of Ar ¹ and Ar ² can be applied.

When the arylene group represented by Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ has a substituent, the substituent is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl It is preferably a C1-C10 alkyl group such as a group, nonyl group, decyl group, etc., a hydroxy group, an amino group, a mercapto group, a carboxyl group, or a sulfo group. However, the ratio of the structural unit of the general formula (20) in which Ar ¹ , Ar ² , Ar ^3, and Ar ⁶ are arylene groups having a substituent suppresses a decrease in crystallinity and heat resistance of the polyarylene sulfide resin. From the viewpoint, the range is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total polyarylene sulfide resin.

  The structural unit possessed by the polyarylene sulfide resin is, for example, a combination of a sulfoxide represented by the general formula (1) and an aromatic compound represented by the general formula (2) in accordance with the purpose of use of the resin. By changing, it can select suitably.

  The glass transition temperature of the polyarylene sulfide resin obtained by the production method of the present embodiment is preferably in the range of 50 to 250 ° C, more preferably in the range of 80 to 180 ° C. The glass transition temperature of the resin indicates a value measured by a DSC apparatus.

  The melting point of the polyarylene sulfide resin obtained by the production method of the present embodiment is preferably in the range of 100 to 400 ° C, and more preferably in the range of 150 to 300 ° C. The melting point of the resin indicates a value measured by a DSC apparatus.

  The halogen content of the polyarylene sulfide resin according to this embodiment is preferably 900 ppm or less, and more preferably 500 ppm or less.

  The Mtop of the polyarylene sulfide resin according to this embodiment is preferably 5,000 to 100,000, and more preferably 10,000 to 80,000. Mw is also in the same range. In this specification, Mtop represents the average molecular weight (peak molecular weight) at the point where the detection intensity of the chromatogram measured by gel permeation chromatography is maximized, and Mw represents the weight average molecular weight.

  Mw / Mtop of the polyarylene sulfide resin according to the present embodiment is in the range of 0.5 to 3.5, preferably in the range of 0.7 to 2.5. By setting Mw / Mtop in such a range, the processability of the polyarylene sulfide resin can be improved, and appropriate stretchability and flexibility can be imparted to the resulting film. Mw / Mtop indicates the distribution of the molecular weight to be measured. Usually, when this value is close to 1, it indicates that the molecular weight distribution is narrow, and as this value increases, the molecular weight distribution is broad. The measurement conditions for gel permeation chromatography are the same as those in the examples of the present specification. However, it is possible to change the measurement conditions within a range that does not substantially affect the values of Mw and Mw / Mtop.

The non-Newtonian index of the polyarylene sulfide resin according to the present embodiment is in the range of 0.5 to 2.3, and preferably in the range of 0.9 to 1.8. By setting the non-Newtonian index in such a range, the processability of the polyarylene sulfide resin can be improved. In the present specification, the non-Newtonian index means an index satisfying the following relational expression between the shear rate and the shear stress under the condition of temperature: melting point + 20 ° C. The non-Newtonian index can be an index related to the molecular weight to be measured or the molecular structure such as linear, branched, or crosslinked. Usually, when this value is close to 1, it indicates that the resin molecular structure is linear. It shows that there are many branched and cross-linked structures as the value increases.
D = α × S ⁿ
(In the above formula, D represents shear rate, S represents shear stress, α represents a constant, and n represents a non-Newtonian index.)

Polyarylene sulfide according to the present embodiment, the FT-IR spectrum as measured by FT-IR spectroscopy (IR ^spectrum), which has an absorption peak in the range of 2910cm ^-1 ~2930cm -1, Thereby, since the solubility with respect to the solvent of a low molecular weight component is favorable, it becomes a polymer which is easy to remove | eliminate by the above-mentioned washing | cleaning process, and has little generated gas amount.
The peak is derived from (belongs to) the stretching vibration of a methylsulfanyl group (-SMe).

  The melt viscosity (V6) at the melting point + 20 ° C. of the polyarylene sulfide resin according to this embodiment is preferably in the range of 1 to 2000 [Pa · s], more preferably in the range of 5 to 1700 [Pa · s]. Here, for the melt viscosity (V6), using a flow tester, an orifice having a temperature of 300 ° C., a load of 1.96 MPa, and a ratio of the orifice length to the orifice diameter (orifice length / orifice diameter) is 10/1. The melt viscosity after holding for 6 minutes.

The whiteness (hot press L value / L ^* value) of the polyarylene sulfide resin according to this embodiment is preferably in the range of 70 to 90, and more preferably in the range of 75 to 85. By setting the L ^* value in such a range, it is possible to obtain a film in which coloring during melt spinning is sufficiently suppressed. The L ^* value is an index related to the whiteness of the measurement target, but can also be an index of oxidative crosslinking. The polyarylene sulfide resin is colored when subjected to a thermal oxidation treatment, and the L ^* value tends to decrease.

  The amount of gas generated during heating of the polyarylene sulfide resin according to the present embodiment can be in the range of 0.2% by mass or less, and preferably in the range of 0.15% by mass or less. Since the amount of gas generated during heating can be suppressed, yarn breakage during spinning can be further suppressed, and deterioration in film quality due to gas generation can be sufficiently suppressed.

  The composition containing the polyarylene sulfide resin can further contain one or more inorganic fillers without departing from the spirit of the present invention. By blending the inorganic filler, high rigidity and high heat stability can be imparted to the film. Examples of inorganic fillers include powder fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate fillers such as talc and mica, granular fillers such as glass beads, silica beads and glass balloons, and glass fibers. And fibrous fillers such as carbon fiber and wollastonite fiber, and glass flakes. It is particularly preferable that the polyarylene sulfide resin composition contains at least one inorganic filler selected from the group consisting of glass fiber, carbon fiber, carbon black, and calcium carbonate.

  The content of the inorganic filler is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 5 to 200 parts by mass, and still more preferably in the range of 15 to 150 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It is. When the content of the inorganic filler is in these ranges, a more excellent effect can be obtained in terms of tensile properties such as tensile strength when formed into a film.

  The polyarylene sulfide resin composition can contain a resin other than the polyarylene sulfide resin selected from thermoplastic resins, elastomers, and crosslinkable resins without departing from the spirit of the present invention. These resins can be blended in the resin composition together with the inorganic filler.

  Examples of the thermoplastic resin blended in the polyarylene sulfide resin composition include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, and polyethylene. , Polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymer (liquid crystal polyester, etc.).

  Polyamide is a polymer having an amide bond (—NHCO—). Examples of the polyamide resin include (i) a polymer obtained from polycondensation of diamine and dicarboxylic acid, (ii) a polymer obtained from polycondensation of aminocarboxylic acid, and (iii) a polymer obtained from ring-opening polymerization of lactam. Is mentioned. Polyamides can be used alone or in combination of two or more.

  Examples of diamines for obtaining polyamides include aliphatic diamines, aromatic diamines, and alicyclic diamines. As aliphatic diamine, C3-C18 diamine which has a linear or side chain is preferable. Examples of suitable aliphatic diamines include 1,3-trimethylene diamine, 1,4-tetramethylene diamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine. 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanmethylenediamine, 1,12-dodecamethylene Diamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18 -Octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine And 2,4,4-trimethyl hexamethylene diamine. These can be used alone or in combination of two or more.

  As the aromatic diamine, a diamine having 6 to 27 carbon atoms having a phenylene group is preferable. Examples of suitable aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4,4′- Diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, 4,4′-di (m-aminophenoxy) Diphenylsulfone, 4,4′-di (p-aminophenoxy) diphenylsulfone, benzidine, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 1 , 5-Diaminonaphthalene, 1,8-diaminonaphthalene 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-diamino-3,3′-diethyl -5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 2,4-diaminotoluene, and 2,2'-dimethylbenzidine. These can be used alone or in combination of two or more.

  As the alicyclic diamine, a diamine having 4 to 15 carbon atoms having a cyclohexylene group is preferable. Examples of suitable alicyclic diamines include 4,4′-diamino-dicyclohexylene methane, 4,4′-diamino-dicyclohexylene propane, 4,4′-diamino-3,3′-dimethyl- Examples include dicyclohexylenemethane, 1,4-diaminocyclohexane, and piperazine. These can be used alone or in combination of two or more.

  Examples of the dicarboxylic acid for obtaining the polyamide include aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and alicyclic dicarboxylic acid.

  As the aliphatic dicarboxylic acid, a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms is preferable. Examples of suitable aliphatic dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, placillic acid, tetradecane Examples include diacids, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid. These can be used alone or in combination of two or more.

  As the aromatic dicarboxylic acid, a dicarboxylic acid having 8 to 15 carbon atoms having a phenylene group is preferable. Examples of suitable aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid. Examples include acids, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. . These can be used alone or in combination of two or more. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range that can be melt-molded.

  As the aminocarboxylic acid, an aminocarboxylic acid having 4 to 18 carbon atoms is preferable. Examples of suitable aminocarboxylic acids include 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. These can be used alone or in combination of two or more.

  Examples of the lactam for obtaining the polyamide include ε-caprolactam, ω-laurolactam, ζ-enantolactam, and η-capryllactam. These can be used alone or in combination of two or more.

  Preferred combinations of polyamide raw materials include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine / adipic acid (nylon 6,6), 1,4-tetramethylenediamine / adipic acid (nylon 4,6) 1,6-hexamethylenediamine / terephthalic acid, 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9-nonamethylenediamine / terephthalic acid Acid, 1,9-nonamethylenediamine / terephthalic acid / ε-caprolactam, 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid, and m-xylylenediamine / adipic acid It is done. Among these, 1,4-tetramethylenediamine / adipic acid (nylon 4,6), 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, Obtained from 1,9-nonamethylenediamine / terephthalic acid, 1,9-nonamethylenediamine / terephthalic acid / ε-caprolactam, or 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid More preferred are amide resins.

  The content of the thermoplastic resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, and still more preferably in the range of 5 to 45 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It is. When the content of the thermoplastic resin other than the polyarylene sulfide resin is within these ranges, the effect of further improving the heat resistance, chemical resistance and mechanical properties can be obtained.

  As the elastomer blended in the polyarylene sulfide resin composition, a thermoplastic elastomer is often used. Examples of the thermoplastic elastomer include polyolefin elastomers, fluorine elastomers, and silicone elastomers. In the present specification, the thermoplastic elastomer is classified not as the thermoplastic resin but as an elastomer.

  The elastomer (particularly thermoplastic elastomer) preferably has a functional group. Thereby, it is possible to obtain a resin composition that is particularly excellent in terms of adhesion and impact resistance. Such functional groups include epoxy groups, amino groups, hydroxyl groups, carboxy groups, mercapto groups, isocyanate groups, oxazoline groups, and the formula: R (CO) O (CO)-or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms.). The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having the functional group. Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, and butene-1. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids and alkyl esters thereof such as (meth) acrylic acid and (meth) acrylic acid esters, maleic acid, fumaric acid, itaconic acid, and the like. Other examples include α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters and acid anhydrides thereof), glycidyl (meth) acrylates, and the like. Among these, an epoxy group, a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms). An ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the represented groups are preferred from the viewpoint of improving toughness and impact resistance.

  Since the elastomer content varies depending on the type and application, it cannot be defined unconditionally. For example, it is preferably in the range of 1 to 300 parts by mass, more preferably 3 to 100 parts per 100 parts by mass of the polyarylene sulfide resin. It is the range of a mass part, More preferably, it is the range of 5-45 mass part. When the content of the elastomer is within these ranges, a more excellent effect can be obtained in terms of securing heat resistance and toughness of the film.

  The crosslinkable resin blended in the polyarylene sulfide resin composition has two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amino group, an amide group, a carboxy group, an acid anhydride group, and an isocyanate group. Examples of the crosslinkable resin include an epoxy resin, a phenol resin, and a urethane resin.

  As the epoxy resin, an aromatic epoxy resin is preferable. The aromatic epoxy resin may have a halogen group or a hydroxyl group. Examples of suitable aromatic epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolacs. Type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl Type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon Le formaldehyde resin-modified phenol resin type epoxy resins, and biphenyl novolac-type epoxy resin. These aromatic epoxy resins can be used alone or in combination of two or more. Among these aromatic epoxy resins, a novolak type epoxy resin is preferable and a cresol novolak type epoxy resin is more preferable because it is excellent in compatibility with other resin components.

  The content of the crosslinkable resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, and still more preferably in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It is. When the content of the crosslinkable resin is within these ranges, the effect of improving the rigidity and heat resistance of the film is obtained particularly remarkably.

  The polyarylene sulfide resin composition can contain a silane compound having a functional group. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples include silane coupling agents such as diethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

  The content of the silane compound is, for example, preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. . When the content of the silane compound is within these ranges, an effect of improving the compatibility between the polyarylene sulfide resin and the other components can be obtained.

  The polyarylene sulfide resin composition according to this embodiment is a mold release agent, a colorant, a heat stabilizer, a UV stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant, and the like without departing from the spirit of the present invention. Other additives may be included. For example, the content of the additive is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin.

  The polyarylene sulfide resin can be obtained in the form of pellets. In addition, the composition containing the polyarylene sulfide resin can be obtained in the form of, for example, a pellet-like compound by a method of melt-kneading the polyarylene sulfide resin and the other components. The melt kneading temperature is, for example, preferably in the range of 250 to 400 ° C, and more preferably in the range of 270 to 380 ° C. Melting and kneading can be performed using a twin screw extruder or the like.

  The film made of the polyarylene sulfide resin according to the present embodiment can be obtained, for example, by forming the resin using a melt extruder.

  First, the pellet-shaped polyarylene sulfide resin obtained by the above-described method is charged into a melt extruder heated at a temperature of the melting part in the range of 250 to 400 ° C, preferably in the range of 270 to 380 ° C, and melted. The polymer is filtered through a filter and discharged from the T die die into a film. By making this film-like material adhere to a cooling drum set so that the surface temperature is in the range of 20 to 70 ° C. and cooling and solidifying, an unstretched film in a substantially non-oriented state can be obtained. . The set temperature of the filter part and the die is preferably set to a temperature range that is 0 to 20 ° C. higher than the temperature of the melt part of the melt extruder, and more preferably set to a temperature range that is 5 to 15 ° C.

  The unstretched film can be biaxially oriented by further performing biaxial stretching or the like. As the stretching method, sequential biaxial stretching method (stretching method in which stretching in the longitudinal direction of the film and stretching in the width direction are separately performed), simultaneous biaxial stretching method (method in which stretching in the longitudinal direction and width direction of the film are performed simultaneously) Is mentioned. These stretching methods may be used in appropriate combination.

  In the sequential biaxial stretching method, an unstretched polyarylene sulfide film is heated by a heated roll group, and the film is stretched by utilizing the difference in rotational speed of the rolls. From the viewpoint of improving the thermoformability of the film, the draw ratio is preferably in the range of 2.0 to 4.0 times in the longitudinal direction (MD direction), and is preferably in the range of 2.5 to 3.5 times. More preferably, it is more preferably in the range of 2.8 to 3.2 times. This stretching step may be performed in one step or in two or more steps.

  The temperature in the stretching process in the MD direction is preferably Tg to (Tg + 30) ° C., when the glass transition temperature of the polyarylene sulfide resin is Tg, and (Tg + 5) to (Tg + 20) ° C. More preferably.

  Examples of the stretching method in the width direction (TD direction) after stretching in the MD direction include a method using a transverse stretching machine (tenter). The both ends of the film after MD stretching are sandwiched between clips, guided to a tenter, and stretched in the TD direction. From the viewpoint of improving the elongation at break of the film, the draw ratio is preferably in the range of 2.0 to 4.0 times in the TD direction, and more preferably in the range of 2.5 to 3.5 times.

  The temperature in the stretching process in the TD direction is preferably in the range of Tg to (Tg + 30) ° C., and more preferably in the range of (Tg + 5) to (Tg + 20) ° C.

  With the film stretched in the TD direction, the stretched film is heat-set and relaxed. The heat setting and relaxation treatment is preferably performed at a temperature in the range of (melting point−30 ° C.) to (melting point + 5). When the thickness of the film is less than 50 μm, the total time for heat setting and relaxation treatment is in the range of 1 to 15 seconds, preferably in the range of 5 to 10 seconds. When the thickness of the film exceeds 50 μm, the total time for heat setting and relaxation treatment is in the range of 10 to 40 seconds, preferably in the range of 20 to 30 seconds. The heat setting and relaxation treatment may be performed in one stage, or may be performed in two or more stages.

  Furthermore, the film can be cooled and rolled up to room temperature, if necessary, in the MD direction and TD direction, if necessary, to obtain the desired biaxially oriented polyarylene sulfide film.

  The 50% elongation at break of the polyarylene sulfide film at 160 ° C. in either the MD or TD direction is preferably 100% or more, more preferably 110% or more, and 120 % Or more is more preferable. The 50% average breaking strength in the MD direction of the polyarylene sulfide film at 160 ° C. is preferably in the range of 30 to 80 MPa, more preferably in the range of 40 to 70 MPa, and in the range of 50 to 60 MPa. It is more preferable.

  The polyarylene sulfide film has a breaking elongation of 100% or more in either the MD direction or the TD direction of the film at 160 ° C., and a breaking stress in either the MD direction or the TD direction of the film at 160 ° C. Is preferably in the range of 30 to 80 MPa. When the breaking elongation and the breaking stress satisfy the above relationship, it is possible to further suppress the occurrence of film breakage during film formation.

  The elongation at break and the stress at break indicate values measured using an Instron type tensile tester according to the method defined in ASTM-D882. A more specific method is to perform a tensile test by sandwiching a sample cut out in a tensile direction with a chuck portion of an upper and lower tensile tester, and when the film sample breaks, the stress is the elongation at break, Measured as the breaking stress. Measurement is performed at 160 ° C. using an Instron type tensile tester on a film having a sample size of 10 mm width × 150 mm length and 100 mm between test lengths at a tensile speed of 300 mm / min.

  The heat shrinkage ratio of the polyarylene sulfide film is preferably 2.5% or less in the MD direction and 4.0% or less in the TD direction when heat-treated at 150 ° C. for 30 minutes. preferable.

  The thickness of the polyarylene sulfide film is not particularly limited, but the lower limit is preferably 100 μm or more, and more preferably 150 μm or more, from the viewpoint of followability during molding. On the other hand, from the viewpoint of film formability, the upper limit is preferably in the range of 1000 μm or less, and more preferably in the range of 500 μm or less. In the present invention, the “film” is not particularly limited in length and width, and is a flat molded product and includes tapes and ribbons. The planar molded product may be referred to as a sheet depending on the thickness. For example, according to a polymer dictionary edited by the Society of Polymer Science (Asakura Shoten, 1971), a film having a thickness of less than 200 μm and a thickness of 200 μm or more is used. The distinction between sheets is described. However, in general, it is difficult to distinguish between a film and a sheet. Therefore, in the present invention, both are collectively referred to as “film”.

  About the said film forming method, it can apply also to the composition containing the said polyarylene sulfide resin.

  The polyarylene sulfide resin composition according to the present embodiment can be used alone or in combination with other materials by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding, heat resistance, molding processability, It can be processed into a molded product having excellent dimensional stability. Since the polyarylene sulfide resin composition according to the present embodiment generates a small amount of gas when heated, it enables easy production of a high-quality molded product.

  The polyarylene sulfide film according to the present embodiment also has various performances such as heat resistance and dimensional stability inherent in the polyarylene sulfide resin. Used as a film used in the fields of automobile parts such as electronic parts, lamp reflectors and various electrical parts, interior materials for various buildings, aircraft and automobiles, precision parts such as OA equipment parts, camera parts and watch parts can do. When used in these applications, the polyarylene sulfide film according to this embodiment may be used alone, or may be used in appropriate combination with other films.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

In the examples shown below, the following reagents were used.
Bis [4- (methylthio) phenyl] sulfide: manufactured by Sigma-Aldrich, product number S203815-25MG
Nitric acid (1.38): manufactured by Wako Pure Chemical Industries, Ltd., reagent grade, content 60-61%, density 1.38 g / mL
Diphenyl sulfide: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade diphenyl ether: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade biphenyl: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade trifluoromethanesulfonic acid: Wako Pure Chemical Industries ( Co., Ltd., Wako Special Grade Methanesulfonic Acid: Wako Pure Chemical Industries, Ltd., Wako Special Grade Phosphorus Oxide (V): Wako Pure Chemical Industries, Ltd., Wako First Grade Pyridine: Wako Pure Chemical Industries, Ltd., Reagent special grade N-methylpyrrolidone: Wako Pure Chemical Industries, Ltd., Wako first grade

<Evaluation method>
1. Evaluation method

1-1. Identification method ( ¹ H-NMR, ¹³ C-NMR)
Measurement was conducted by dissolving in various heavy solvents using a DPX-400 apparatus manufactured by BRUKER.

1-2. Analysis of residual halogen content The powder was measured with fluorescent X-rays (ZSX100e manufactured by Rigaku Corporation), and the residual halogen content was analyzed.

2. Monomer synthesis

In a 10 L three-necked flask, 20.0 [g] of bis [4- (methylthio) phenyl] sulfide and 5 [L] of dichloromethane were added and dissolved, and cooled in an ice bath. Nitric acid (1.38) 14 [mL] was added dropwise little by little, and the mixture was stirred at room temperature for 72 hours. The mixture was neutralized with an aqueous potassium carbonate solution and extracted / separated with dichloromethane to recover the organic layer. The organic layer was dried over anhydrous magnesium sulfate. After filtration, the solvent was removed with a rotary evaporator and dried under reduced pressure to obtain a crude product. Separation by column chromatography using ethyl acetate as a developing solvent, the target product is recovered, the solvent is removed by a rotary evaporator, and dried under reduced pressure to obtain 6.7 g of bis [4- (methylsulfinyl) phenyl] sulfide. 30%). It was confirmed that the target product was obtained by ¹ H-NMR measurement. Moreover, it was confirmed by the analysis with fluorescent X-rays that the residual halogen amount was outside the detection range.
¹ H-NMR (solvent CDCl ₃ ): 2.75, 7.49, 7.61 [ppm]

3. Evaluation method of synthesized polyarylene sulfide resin

3-1. Glass Transition Temperature and Melting Point Using a Perkin Elmer DSC device Pyris Diamond, measurement was performed from 40 to 400 ° C. under a temperature rise condition of 20 ° C./min under a nitrogen flow of 50 mL / min to obtain a glass transition temperature and a melting point.

3-2. Infrared absorption spectrum The obtained PPS resin was pressed at a temperature of melting point + 50 ° C., and then rapidly cooled to prepare a film showing non-crystalline properties, and abbreviated as a Fourier transform infrared spectrometer (hereinafter referred to as “FT-IR apparatus”). FTIR-6100 manufactured by JASCO Corporation was used.)

3-3. Melt viscosity of polyarylene sulfide resin Using polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500C, at a temperature of melting point + 20 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10/1 The melt viscosity was measured after holding for 6 minutes.

3-4. Mw and Mtop (Molecular weight distribution)
The weight average molecular weight and peak molecular weight of the polyarylene sulfide resin were measured under the following measurement conditions using gel permeation chromatography. Mw / Mtop was calculated from the obtained Mw and Mtop. Six types of monodisperse polystyrene were used for calibration.
Apparatus: Ultra-high temperature polymer molecular weight distribution measuring apparatus (“SSC-7000” manufactured by Senshu Scientific Co., Ltd.)
Column: UT-805L (made by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene Measurement method: UV detector (360 nm)

3-5. Halogen content The chlorine content in the polymer was determined by absorbing the gas generated by burning the polymer with a Diane Instruments combustion gas absorption device into pure water, and quantifying the chlorine ions in the absorption solution with a Dionex ion chromatograph.

3-6. Color tone L ^* value Whiteness (hot press L ^* value) was determined by preheating the polyarylene sulfide resin at 320 ° C. for 1.5 minutes, then at 320 ° C. for 1.5 minutes, then at 130 ° C. for 1.5 minutes, 30 kg / A disk-shaped plate was produced by pressure molding with a hot press at a pressure of cm ² . About this, it measured using the color difference meter (The Tokyo Denshoku Co., Ltd. make, Color Ace).

3-7. Non-Newtonian index Polyarylene sulfide resin was measured with a capillary rheometer using a die with a diameter of 1 mm and a length of 40 mm under conditions of temperature: melting point + 20 ° C. and shear stress for a shear rate of 100 to 1000 (sec ⁻¹ ). It is a value measured and calculated from the slopes of these logarithmic plots.

3-8. Generated Gas Amount Using a gas chromatograph mass spectrometer, a predetermined amount of a sample of polyarylene sulfide resin or resin composition was heated at 325 ° C. for 15 minutes, and the amount of generated gas at that time was determined as mass%.

4). Synthesis of polyarylene sulfide resin

Synthesis example 1

In a 500 mL separable flask, 0.932 [g] of bis [4- (methylsulfinyl) phenyl] sulfide is placed, put under a nitrogen atmosphere, 0.560 [g] of diphenyl sulfide is added, and 1 [g] of phosphorus oxide is further added. Was added. After cooling in an ice bath, methanesulfonic acid 5 [mL] was slowly added dropwise. The mixture was warmed to room temperature and stirred for 20 hours. The reaction solution was put into water, stirred for 10 minutes, filtered, washed with water and filtered to collect a solid. The solvent was removed with a rotary evaporator and dried under reduced pressure to obtain 2.25 [g] (99% yield) of poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium].
A small amount of the sample was collected for analysis, and ¹ H-NMR measurement was performed on the sample dissolved in heavy DMSO to confirm that the target product was synthesized.
¹ H-NMR (solvent weight DMSO): 3.27, 3.93, 7.76, 8.19 [ppm]

Poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium] 2.00 [g] is placed in a 100 mL eggplant flask, pyridine 100 [mL] is added, and the mixture is stirred at room temperature for 30 minutes, and then heated to 110 ° C. And stirred for 20 hours. The reaction solution was cooled to room temperature and then poured into water, and the precipitate was filtered off and washed with chloroform, NMP and water. After washing, the solid was dried under reduced pressure to obtain 0.64 [g] (yield 56%) of polyphenylene sulfide.
As a result of conducting a thermal analysis on the obtained resin, the glass transition temperature (Tg) was 93 ° C. and the melting point was 273 ° C.
Further, when the infrared absorption spectrum was measured, the presence of an absorption peak was recognized at the position (OK) at 2917 cm ⁻¹ as shown in FIG.
Further, the melt viscosity of this polymer was 1430 Pa · s, Mtop was 57000, and Mw was 60000.
In addition, the halogen content was found to be significantly reduced to 50 ppm or less.
The L value was 74 and the non-Newtonian index was 1.2.
The amount of generated gas was as small as 0.1 [wt%].

Synthesis example 2

In a 500 mL separable flask, 0.932 [g] of bis [4- (methylsulfinyl) phenyl] sulfide was placed, put under a nitrogen atmosphere, and 0.511 [g] of diphenyl ether was added. After cooling in an ice bath, trifluoromethanesulfonic acid 7.5 [mL] was slowly added dropwise. The mixture was warmed to room temperature and stirred for 20 hours. The reaction solution was put into water, stirred for 10 minutes, filtered, washed with water and filtered to collect a solid. By removing the solvent with a rotary evaporator and drying under reduced pressure, poly [trifluoromethylsulfonic acid methyl (4-phenyloxyphenyl) sulfonium-4′-methyl (4-phenylthiophenyl) sulfonium] 2.19 [g] ( Yield 98%).
A small amount of the sample was collected for analysis, and after ion exchange with an excess of methanesulfonic acid, ¹ H-NMR measurement was performed on what was dissolved in heavy acetic acid to confirm that the target product was synthesized. .
¹ H-NMR (solvent biacetic acid): 3.17, 3.92, 7.61, 7.87, 8.08, 8.18 [ppm]

Poly [trifluoromethanesulfonic acid methyl (4-phenyloxyphenyl) sulfonium-4′-methyl (4-phenylthiophenyl) sulfonium] 2.00 [g] is placed in a 100 mL eggplant flask, and pyridine 100 [mL] is added. The mixture was stirred at room temperature for 30 minutes, heated to 110 ° C., and stirred for 20 hours. The reaction solution was cooled to room temperature and then poured into water, and the precipitate was filtered off and washed with chloroform, NMP and water. After washing, the solid was dried under reduced pressure to obtain 0.54 [g] (yield 48%) of poly [(phenylene ether)-(phenylene sulfide)].
As a result of thermal analysis of the obtained resin, it had a glass transition temperature (Tg) of 96 ° C. and a melting point of 229 ° C.
Moreover, when the infrared absorption spectrum was measured, the presence of an absorption peak was observed at a position of 2918 cm ⁻¹ as shown in FIG.
Further, the melt viscosity of this polymer was 100 Pa · s, Mtop was 10,000, and Mw was 12,000.
In addition, the halogen content was found to be significantly reduced to 50 ppm or less.
The L value was 72 and the non-Newtonian index was 1.5.
The amount of generated gas was as small as 0.05 [wt%].

Synthesis example 3

Instead of diphenyl ether, poly [trifluoromethylsulfonic acid methyl (4-phenylthiophenyl) sulfonium-4′-methyl (4-biphenyl) was synthesized in the same manner as in Synthesis Example 2 except that biphenyl 0.463 [g] was used. ) Sulfonium] 2.08 [g] (yield 95%).
A small amount of the sample was taken for analysis, and after ion exchange with an excess of methanesulfonic acid, ¹ H-NMR measurement was performed on what was dissolved in deuterated acetonitrile to confirm that the target product was synthesized. .
1H-NMR (deuterated acetonitrile): 3.32, 3.58, 7.45, 7.66, 7.78, 7.95 [ppm]

Poly [methyl trifluoromethanesulfonate (4-phenylthiophenyl) sulfonium-4′-methyl (4-biphenyl) sulfonium] 1.80 [g] was placed in a 100 mL eggplant flask, pyridine 100 [mL] was added, and room temperature was added. After stirring for 30 minutes, the temperature was raised to 110 ° C. and stirred for 20 hours. The reaction solution was cooled to room temperature and then poured into water, and the precipitate was filtered off and washed with chloroform, NMP and water. After washing, the solid was dried under reduced pressure to obtain 0.87 [g] (yield 88%) of poly [(phenylene sulfide)-(biphenylene sulfide)].
As a result of thermal analysis of the obtained resin, the glass transition temperature (Tg) was 127 ° C. and the melting point was 325 ° C.
Moreover, when the infrared absorption spectrum was measured, the presence of an absorption peak was observed at a position of 2917 cm ⁻¹ as shown in FIG.
Further, the melt viscosity of this polymer was 330 Pa · s, Mtop was 16000, and Mw was 18000.
In addition, the halogen content was found to be significantly reduced to 50 ppm or less.
The L value was 75 and the non-Newtonian index was 1.3.
The amount of generated gas was as small as 0.1 [wt%].

Comparative Synthesis Example 220.5 g of p-dichlorobenzene (hereinafter abbreviated as “p-DCB”) in a 1 liter autoclave of zirconium lining with stirring blades connected with a pressure gauge, a thermometer, a condenser and a decanter. 5 mol), 29.7 g (0.3 mol) of NMP, 177.29 g (1.5 mol) of 47.43 wt% aqueous NaOH solution, and 123.18 g (1.5 mol) of 48.71 wt% aqueous NaOH solution While stirring, the temperature was raised to 173 ° C. over 2 hours under a nitrogen atmosphere to distill 177.98 g of water, and the kettle was sealed. At that time, p-DCB distilled by azeotropic distillation was separated by a decanter and returned to the inside of the kettle as needed. After completion of dehydration, the internal temperature was cooled to 160 ° C., 267.65 g (2.7 mol) of NMP was charged, the temperature was raised to 230 ° C., stirred at 230 ° C. for 5 hours, and then heated to 250 ° C. in 40 minutes. , And stirred at 250 ° C. for 1 hour. After cooling, the resulting slurry was poured into 3 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred with 3 liters of warm water for 1 hour, washed and filtered. This operation was repeated 4 times, and after filtration, it was dried overnight at 120 ° C. using a hot air dryer to obtain 154 g of white powdery PPS.
As a result of conducting a thermal analysis on the obtained solid, it was confirmed that a polyphenylene sulfide resin (PPS resin) was produced because it had a glass transition temperature (Tg) of 92 ° C. and a melting point of 277 ° C.
The measured infrared absorption spectrum, as shown in FIG. ^4, the presence of absorption peak in the range of 2910cm ^-1 ~2930cm -1 did et al observed.
Further, this polymer had a melt viscosity of 220 Pa · s, Mtop of 45000, and Mw of 44,000.
The halogen content was 1700 ppm.
The L value was 77 and the non-Newton index was 1.1.
The amount of generated gas was 0.5 [wt%].

5). Production and Evaluation of Polyarylene Sulfide Film After the white powdery polymers obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example were uniformly mixed using a tumbler, a twin-screw kneading extruder (TEM-35B, Toshiba Machine) Was melt-kneaded at a melting point of + 20 ° C. to obtain a pellet-shaped polymer. The obtained pellets were supplied to an extruder whose melting part was heated to the melting point + 40 ° C. The polymer melted by the extruder is filtered through a filter set at a temperature: melting point + 50 ° C., and then melt extruded from a base set at a temperature: melting point + 30 ° C. An unstretched film was produced by cooling and solidifying.
This unstretched film was used in the machine direction of the film at a glass transition temperature of + 20 ° C. at a film temperature of + 20 ° C. by using the difference in the winding speed of the roll after using Yonazu, using a longitudinal stretching machine composed of a plurality of heated roll groups. 3. Stretched at a stretch ratio of 2 times. Thereafter, both ends of the film are held with clips and guided to a transverse stretching machine (tenter), and stretched in the width direction of the film at a stretching temperature glass transition temperature of + 20 ° C. and a stretching ratio of 3.3 times. : Heat treatment for 4 seconds (first stage heat treatment) at glass transition temperature + 100 ° C., followed by heat treatment for 4 seconds (second stage heat treatment) at a melting point of −40 ° C. Subsequently, after 5% relaxation treatment in the transverse direction for 4 seconds in a relaxation treatment zone having a melting point of −20 ° C., the film edge was removed after cooling to room temperature, and a biaxially oriented polyarylene sulfide film having a thickness of 100 μm was produced. did.

The obtained biaxially oriented polyarylene sulfide film was evaluated for tensile properties, thermal shrinkage, processing properties, and the like. The evaluation results are shown in Table 1.
In addition, Example 1 using the polymer of Synthesis Example 1, Example 2 using the polymer of Synthesis Example 2, Example 3 using the polymer of Synthesis Example 3, and Polymer of Comparative Synthesis Example What was used is described as Comparative Example 1.

5-1. Tensile properties (160 ° C, 50% average breaking stress, 160 ° C, 50% average breaking elongation)
According to the method prescribed | regulated to ASTM-D882, it measured using the Instron type tensile tester. The measurement was performed under the following conditions, and with 10 samples, an average value was taken for each of the film longitudinal direction and the width direction, and 50% average breaking stress and 50% average breaking elongation were calculated by the following formulas.
50% average breaking stress = (average value of stress in the film longitudinal direction + average value of stress in the film width direction) / 2
50% average breaking elongation = (average elongation in the film longitudinal direction + average elongation in the film width direction) / 2
Measuring device: Orientec Co., Ltd. film strong elongation automatic measuring device “Tensilon AMF / RTA-100”
Sample size: width 10 mm ×× length 150 mm, sample length 100 mm
Pulling speed: 300mm / min

5-2. Thermal contraction rate It measured according to the method prescribed | regulated to JISC-2318. A sample having a sample width of 10 mm and a sample length of 200 mm was heat-treated in a gear oven at 150 ° C. for 30 minutes, and the heat shrinkage rate was calculated from the change in the sample length by the following formula.
Thermal shrinkage rate (%) = [(length before heat treatment−length after heat treatment) / length before heat treatment] × 100

5-3. Processing characteristics The elongation at break in either the longitudinal direction or the width direction of the film at 160 ° C. is 100% or more, and the breaking stress in either the longitudinal direction or the width direction of the film at 160 ° C. is 30 to 80 MPa. Only when it was in the range, the processing characteristics were “◯”, and the other cases were processing characteristics “x”.

5-4. Film breakage during film formation Film breakage during film formation is “x” when film breakage occurs 5 times or more when continuous film formation is performed for a total time of 24 hours, and film breakage is 1 time or more and less than 5 times The case where it occurred in the range of “Δ” was designated as “Δ”, and the case where no film breakage occurred was designated as “◯”.

In Examples 1 to 3, compared with Comparative Example 1, the amount of halogen is much smaller and the amount of generated gas is also smaller.
Further, as is apparent from the results shown in the table, Examples 1 to 3 have high tensile properties and inherent properties of the polyarylene sulfide resin such as a sufficiently small heat shrinkage rate, and film breakage during film formation. Was suppressed, and it was confirmed that the processing characteristics were also excellent.

Claims (3)

Having a step of forming a polyarylene sulfide resin or a composition containing the same,
The polyarylene sulfide resin reacts with a sulfoxide represented by the following general formula (1) and an aromatic compound represented by the following general formula (2) to form a structural unit represented by the following general formula (10). Obtaining a poly (arylenesulfonium salt) having:
Dealkylating or dearylating the poly (arylenesulfonium salt) to obtain a polyarylene sulfide resin having a structural unit represented by the following general formula (20);
Can be obtained by a method comprising
The polyarylene sulfide resin has —S—R ¹ ;
Method for producing a port Leary sulfide film.

(In Formula (1), (2), (10) or (20), R ¹ is an aryl optionally having an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. R ^2a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, —Ar ⁴ , —S—Ar ⁴ , —O—Ar ⁴ , —CO—Ar ⁴ , —SO ₂ —Ar ⁴ or represents ^{_{-C (CF 3) 2 -Ar 4}} , R 2b is a direct ^{bond, -Ar 6 -, - S-} Ar 6 -, - O-Ar 6 -, - CO-Ar 6 -, - SO 2 - Ar ⁶ — or —C (CF ₃ ) ₂ —Ar ⁶ — is represented, Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ each independently represent an arylene group which may have a substituent, Ar ^3a and Ar ⁴ each independently represent an aryl group which may have a substituent, Z is a direct bond, - -, - O -, - CO -, - SO 2 - or -C _{(CF 3) 2} - represents, X ^- represents an anion).   The method for producing a polyarylene sulfide film according to claim 1, wherein the polyarylene sulfide resin has a methylsulfanyl group. The polyarylene sulfide resin, the infrared absorption spectrum measured by FT-IR spectroscopy, and has an absorption peak based on -S-R ^1, the production method of polyarylene sulfide film according to claim 1 .

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